Sterilant composition

ABSTRACT

A biocidal, aqueous composition for killing bacteria, spores, fungi, and viruses on nonabsorbent surfaces comprises at least one quaternary ammonium compound, at least one aliphatic dialdehyde having from two to six carbon atoms, and at least one aliphatic hydroxyl compound having form one to eight carbon atoms. 
     This sterilant is stable for weeks, is especially useful between pH 4 to 9, and may additionally comprise a chelating agent.

RELATED U.S. APPLICATIONS

This application is a continuation under rule 62 of application Ser. No.07/866,010, filed Apr. 9, 1992, now abandoned, and said application is acontinuation of 758,400, Aug. 27, 1991, (now U.S. Pat. No. 5,124,359);which is a continuation-in-part of 210,626, Jun. 23, 1988 (now U.S. Pat.No. 4,923,899); which is a continuation-in-part of 139,166, Dec. 22,1987 (now abandoned); which is a continuation of 906,557, Sep. 8, 1986now abandoned; which is a continuation of 776,479, Sep. 16, 1985, nowabandoned; which is a continuation of 692,776, Jan. 18, 1985 (nowabandoned).

FIELD OF THE INVENTION

This invention relates to a broad-spectrum biocidal compositioneffective for the rapid killing of a wide variety of bacteria, spores,fungi, and viruses on a wide variety of nonabsorbent surfaces such asmetals, plastics, resins, woods, rubbers, ceramics, and glasses. Thecomposition of the present invention kills so many organisms on such awide variety of surfaces that it may be termed a sterilant.

Some of the articles which may be sterilized by the composition of thepresent invention are counters, floors, sheets, catheters, dialysismachine tubing, anesthetic breathing bags, surgical instruments, dentalbite blocks, saliva-draining tubes, respirator equipment, andenvironmental surfaces in general.

BACKGROUND OF THE INVENTION

In the past in medical and dental circles, steam sterilization ortreatment with ethylene oxide in a closed apparatus have been consideredideal ways of sterilizing equipment. But for many types or parts ofapparatus, steam sterilization is impractical because of the size ornumber of items to be sterilized. For parts of equipment which actuallycome in contact with the patient, such as dental bite blocks, anestheticbreathing bags, respirators, etc. it is impermissible for ethylene oxideto be used because residual trace amounts might harm the patient.

Hence, a stable, benign, broad-spectrum sterilant effective at a widerange of pH's is greatly desired by the medical/dental profession forenvironmental use, especially on nonabsorbent surfaces.

A disinfectant is generally considered to be an agent which destroysbacterial organisms which are growing, but not bacterial spores.Germicide and bactericide are approximately synonymous withdisinfectant. An antiseptic inhibits the growth of microorganisms. Asporicide kills spores of fungi molds, and bacteria. Since spores aremore resistant than bacteria, sporicides are generally consideredsterilizing agents. Biocides kill all living microorganisms, hence alsoare sterilizing agents. A virucide kills viruses; a fungicide killsfungi. The novel sterilant of this invention kills bacteria, spores,fungi and viruses. Hence, it may be termed a biocide or a sterilant.

The Hamilton U.S. Pat. No. 3,208,936, discloses combining a broad rangeof quaternary amines as germicides and foaming agents in recirculationtype toilets.

The Halley U.S. Pat. No. 3,785,971, is directed to a waste treatmentmaterial for a storage holding tank in which paraformaldehyde and analkali carbonate or hydroxide are combined.

U.S. Pat. No. 2,998,390, granted Aug. 29, 1961 to Hamilton and U.S. Pat.No. 3,107,216, granted Oct. 15, 1963 to Hamilton, disclose arecirculating toilet fluid which contains a quaternary ammonium salt.

"Quaternary Ammonium Salts as Germicidals. Nonacylated QuaternaryAmmonium Salts Derived from Aliphatic Amines," Shelton, R. S. et al.,Journal of the American Chemical Society, vol. 68, pp. 753-55 (1946),reported that alkyl quaternary ammonium salts have germicidal powers andN-benzyl substitutes do not affect this germical activity.

It was reported in Gardner, J. Disinfection, Sterilization &Preservation, p. 900, S. S. Block, ed., Lea & Febiger, 2nd ed. (1977) toinclude chelating agents with phenols and certain quaternary ammoniumsalts for enhanced activity against Gram-negative bacteria.

The Schattner U.S. Pat. No. 4,103,001 discloses an aqueous mixture ofphenol, sodium tetraborate, and sodium phenate solution to which isadded aqueous glutaraldehyde in order to kill some bacteria andbacterial spores. This mixture cannot be used against fungi or viruses.

The Stonehill U.S. Pat. No. 3,282,775 discloses a mixture of dialdehydesand a cationic surface active agent, plus a lower alcohol, which killsfour spore-forming bacteria, but not fungi or viruses.

The Pepper U.S. Pat. No. 3,016,328 discloses that simple dialdehydesplus a lower alkanol to the extent of about 60 to 70% and analkalinizing agent to yield a pH range of about 8 to 9.5 kill fourspore-forming bacteria, two of which are the same as in U.S. Pat. No.3,282,775.

Borick, et al in the Journal of Pharmaceutical Sciences, Vol. 53, No. 10at p. 1273 disclose that glutaraldehyde alkalinized with sodiumbicarbonate kills eight nonspore-forming bacteria, four spore-formingbacteria, one fungus, and nine viruses, but that this alkaline solutionwas stable only for about two weeks.

French Patent 2,321,300 discloses that a mixture of aldehyde andquaternary ammonium compound has antiseptic properties by reducing thegrowth of five bacteria of interest to the food industry.

British Patent 1,443,786 discloses that a mixture of glutaraldehyde, alower alcohol, and a highly ionizable salt at acidic pH ranges killsfour sporulating bacteria by ion-exchange with the calcium in the wallsof the bacterial spores.

The Wagner U.S. Pat. No. 4,107,312 discloses a disinfectant mixture of astrong formaldehyde solution, plus minor amounts of glyoxal andglutaraldehyde, plus a quaternary ammonium salt, methanol to stabilizethe formaldehyde, a nonionic wetting agent, optionally some alcohol orglycol, and a scent, all at a neutral pH in order to avoid corrosion ofaluminum toilets (or minimize corrosion of magnesium toilets) inaircraft.

The Mandt U.S. Pat. No 4,444,785 discloses a disinfecting solution forsoft contact lenses against two nonsporulating bacteria comprising avery low concentration of 1,5 pentanedial at neutral pH compatible withthe human eye.

The Schaeufele U.S. Pat. No. 4,320,147 discloses a germicidalcomposition comprising quaternary ammonium chlorides, plus buildersalts, which are useful for disinfection against bacteria.

Canadian Patent No. 1,154,555 discloses a bactericide compositioncontaining formaldehyde, glutaraldehyde and a quaternary ammoniumingredient.

French Patent No. 2,145,444 discloses a bactericide compositioncontaining formaldehyde and a quaternary ammonium compound.

The Lockwood U.S. Pat. No. 3,505,690 relates to a disinfectantdispersing system.

The Buchalter U.S. Pat. No. 3,983,252 discloses a chemical disinfectingcomposition comprising a dialdehyde and an alkali metal salt of ahydrocarbon carboxylic acid and optionally an alcohol.

The Goldhaft U.S. Pat. No. 4,022,911 discloses a disinfectantcomposition comprising three essential active ingredients, namely adimethyl quaternary ammonium halide salt, a phenol or derivativethereof, and formaldehyde.

Oshchepkova and Kochkin in the Proceedings of the First All-UnionConference on Biocorrosion, Biodamage, and Marine Encrustation (1975),C.A.91:69799p report that a mixture of organotin fumarates oracryloyloxy stannate mixed with N-alkyl pyridinium salts ortetraalkylammonium salts protect wood samples in water from two commonbacteria - A. niger and P. purpureum.

OBJECTS OF THE INVENTION

It is an object of this invention to provide a stable, benign,nonodorous, solution which kills a broad-spectrum of bacteria, spores,fungi, and viruses rapidly at a wide range of pH.

It is a further object of this invention to provide a broad-spectrumsterilant which will remain an active solution for at least severalweeks.

It is yet another object of this invention to provide a sterilant whichis effective on hard, nonabsorbent, "environmental" surfaces such asanesthetic breathing bags, dialysis tubing, respirators, dental biteblocks, saliva-draining tubes, and the like for which sterilization bysteam or ethylene oxide is either impractical or physiologicallydisfavored.

It is an object of the present invention to provide a sterilantcomposition effective for killing rapidly individual microorganisms or acombination of several different kinds of microorganisms, such asbacteria, spores, fungi and/or viruses.

Another object of the invention is to provide a sterilant for a widevariety of hard surfaces such as metals, plastics, resins, rubbers,ceramics, and glasses.

Yet another object of the present invention is to provide a sterilantwhich is effective in the presence of high concentrations of blood,sputum, feces, urine, vomitus, and other animal exudates.

Other objects of the present invention will be apparent to those skilledin the art.

SUMMARY OF THE INVENTION

Surprisingly, a broad-spectrum sterilant capable of rapidly killingbacteria, sporulating bacteria, spores, fungi, and viruses can beachieved by combining in an aqueous solution an effective amount of atleast one quaternary ammonium compound, at least one aliphaticdialdehyde having from two to six carbon atoms, and at least onealiphatic hydroxyl compound having from one to eight carbon atoms.

Another aspect of the invention relates to the use of the novelsterilant on "hard" or "environmental" surfaces (nonabsorbing) such asmedical or dental equipment for which previously steam sterilization ortreatment with ethylene oxide were employed.

The sterilant of the present invention relates to a liquid compositionwhich is effective for rapidly killing at least one microorganism or anycombination of two or more different microorganisms such as bacteria,spores, fungi and viruses.

For still another aspect of the invention, the novel sterilant isemployed over a wide range of pH and is stable for several weeks afterhaving been compounded.

Yet another aspect of the present invention arises from its efficacy inthe presence of high concentrations of blood, sputum, urine, feces,vomitus or other bodily liquids or suspensions.

A further aspect of the present invention is its efficacy in sterilizinghard surfaces of metals, plastics, rubbers, resins, wood, ceramics, orglasses.

A typical embodiment of the invention comprises:

    ______________________________________                                        Component               Weight %                                              ______________________________________                                        Alkylbenzyldimethylammonium chloride                                                                  0.1                                                   Cetyldimethylethylammonium bromide                                                                    0.1                                                   Glutaraldehyde          2.6                                                   Isopropyl alcohol       0.2                                                   Propylene glycol        0.16                                                  Sodium nitrite          0.11                                                  Tetrasodium ethylenediamine tetraacetate                                                              0.015                                                 Water                   balance                                               ______________________________________                                    

Processes for employing these sterilant compositions are also disclosedherein.

DETAILED DESCRIPTION OF THE INVENTION

As discussed above, the prior art discloses individual compounds ormixtures of compounds which kill or inhibit the growth of a narrow rangeof organisms such as some bacteria, spores, fungi, or viruses. Thesynergistic combination of the seven components of the present inventionunexpectedly kills all types of the names organisms, hence it is asterilant. Among the classes of organisms killed by the composition ofthe present invention alone or admixed together are Gram-negativebacteria, Gram-positive bacteria, algae, protozoa, Gram-positivespore-forming bacteria, fungi, and many types of viruses.

Among the many typos of viruses killed by the composition of the presentinvention are: orbiviruses, orthomyxoviruses, papovaviruses,paramyxoviruses, parvoviruses, picornaviruses, poxviruses,coronaviruses, flaviviruses, herpesviruses, adenoviruses, arenaviruses,bunyaviridae, caliciviruses, reoviruses, retioviruses, rhabdoviruses,rotaviruses, togaviruses, and various unclassified viruses, plus plantviruses.

In addition to the bacteria, spores, protozoa, algae, fungi, and virusescategorized above, the composition of the present invention can killalone or in combination with the other organisms typified above variousmiscellaneous organisms from the Chlamydia Coxiella, Ehrlichia,Rickettsia, Rochalimaea, Wolbachia, and Thai tick typhus.

It is to be emphasized that the composition of the present invention isa sterilant which can kill any or all of the types of organismsdescribed here alone or in any combination.

At the end of the Examples of this specification and before the claims,several hundred representative specific organisms are listed in Tables Ito VII on which the synergistic composition of the present invention iseffective.

The cationic, quaternary salts useful in the present invention maycontain either or both of aliphatic and aromatic moieties. Althoughquaternary ammonium salts are preferred, cationic phosphonium, orsulfonium, or any other positive nonmetallic nuclei may be selected.Some of the aliphatic or alicyclic substituents for the quaternary ionsare alkyl groups containing one to 30 carbon atoms both linear andbranched, alkoxy groups also containing one to 30 carbon atoms bothlinear and branched, alicyclic groups such as cyclohexyl and itsalkylated or alkyloxylated derivatives, and halogenated alkyl,halogenated alicyclic, or halogenated alkyloxy derivatives.

Aromatic moieties, which may themselves be substituted by aliphatic,alicyclic, alkyloxy groups, useful as substituents for the quaternarycationic salts of the present invention are benzyl, tolyl, xylyl,naphthyl, pyridyl, benzal, quinolyl and the like.

More specifically, some aliphatic quaternary ammonium salts which areuseful in the present invention are: tetramethyl ammonium halide,trimethylethyl ammonium halide, dimethyldiethyl ammonium halide,methyltriethyl ammonium halide, tetraethyl ammonium halide,cetyldimethylethyl ammonium halide, trimethyln-propyl ammonium halide,dimethyldin-propyl ammonium halide, methyltrin-propyl ammonium halide,tetran-propyl ammonium halide, methylethyln-propyln-butyl ammoniumhalide, ethyln-propyln-pentyl ammonium halide, trimethylallyl ammoniumhalide, dimethyldiallyl ammonium halide, methyltriallyl ammonium halide,tetraallyl ammonium halide, N,N,N,N',N',N'-hexaethyl-1,2-ethylenediammoniumhalide, N,N,N,N',N',N'-hexaethyl-1,4-butylenediammoniumhalide, N,N,N'-dibenzyl-N,N,N',N', tetramethyl-1,2-ethylene diammoniumhalide, N,N'-di(4-chlorobenzyl)-N,N,N',N'-tetramethyl-1,2-ethylenediammoniumhalide, N,N,N'-tetraethyl-N,n"-dioctadecyl-1,2-ethylenediammonium halide, N,N,N',N'-tetraethyl-N,N'-dihexadecyl-1,4-butylenediammonium halide, octadecyltrimethyl ammonium halide,dioctadecyldimethyl ammonium halide, trioctadecylmethyl ammonium halidetetraoctadecyl ammonium halide, hexadecyltriethyl ammonium halide,hexadecyldimethylethyl ammonium halide, hexadecyldiethylmethyl ammoniumhalide, didecyldioctyl ammonium halide, didecyldihexyl ammonium halide,and hexyloctyldecyldodecyl ammonium halide.

Some representative useful quaternary ammonium salts containing anaromatic moiety include: benzylodecyldimethyl ammonium halide,o-tolyldodecyldimethyl ammonium halide, m-tolyldodecyldimethyl ammoniumhalide, p-tolyldodecyldimethyl ammonium halide, 2,3-xylyldodecyldimethylammonium halide, 2,4-xylydodecyldimethyl ammonium halide,2,5-xylyldodecyldimethyl ammonium halide, 3,4-xylyldodecyldimethylammonium halide, 3,5-xylyldodecyldimethyl ammoniuim halide,2-chlorobenzyldodecyldimethyl ammonium halide,3-chlorobenzyldodecyldimethyl ammonium halide,4-chlorobenzyldodecyldimethyl ammonium halide,2,3-dichlorobenzyldodecyldimethyl ammonium halide,2,4-dichlorobenzyldodecyldimethyl ammonium halide,2,5-dichlorobenzyldodecyldimethyl ammonium halide,2,6-dichlorobenzyldodecyldimethyl ammonium halide,3,4-dichlorobenzyldodecyldimethyl ammonium halide,3,5-dichlorobenzyldodecyldimethyl ammonium halide,2-nitrobenzyldodecyldimethyl ammonium halide,3-nitrobenzyldodecyldimethyl ammonium halide,4-nitrobenzyldodecyldimethyl ammonium halide,2,4-dinitrobenzyldodecyldimethyl ammonium halide,3,5-dinitrobenzyldodecyldimethyl ammonium halide,2-sulfobenzyldodecyldimethyl ammonium halide,3-sulfobenzyldodecyldimethyl ammonium halide,4-sulfobenzyldodecyldimethyl ammonium halide,2-carboxybenzyldodecyldimethyl ammonium halide,3-carboxybenzyldodecyldimethyl ammonium halide,4-carboxybenzyldodecyldimethyl ammonium halide, benzylhexyldimethylammonium halide, benzyloctyldimethyl ammonium halide,benzyldecyldimethyl ammonium halide, benzyldodecyldimethyl ammoniumhalide, benzyltetradecyldimethyl ammonium halide,benzylhexadecyldimethyl ammonium halide, benzyloctadecyldimethylammonium halide.

Some representative, useful quaternary ammonium salts containingheterocyclic, aromatic moieties include: n-hexylpyridinium halide,n-octylpyridinium halide, n-decylpyridinium halide, n-dodecylpyridiniumhalide, n-tetradecylpyridinium halide, n-hexadecylpyridinium halide,n-hexyllutidinium halide, n-octyllutidinium halide, n-decyllutidiniumhalide, n-dodecyllutidinium halide, n-tetradecyllutidinium halide,n-hexadecyllutidinium halide, n-hexylpicolinium halide,n-octylpicolinium halide, n-decylpicolinium halide, n-dodecylpicoliniumhalide, n-tetradecylpicolinium halide, n-hexadecylpicolinium halide,n-hexylquinolinium halide, n-octylquinolinium halide, n-decylquinoliniumhalide, n-dodecylquinolinium halide, n-tetradecylquinolinium halide,n-hexadecylquinolinium halide, n-hexylisoquinolinium halide,n-octylisoquinolinium halide, n-decylisoquinolinium halide,n-dodecylisoquinolinium halide, n-tetradecylisoquinolinium halide,n-hexadecylisoquinolinium halide, n-hexylquinazolinium halide,n-octylquinazolinium halide, n-decylquinazolinium halide,n-dodecylquinazolinium halide, n-tetradecylquinazolinium halide,n-hexadecylquinazolinium halide, n-hexylquinoxalinium halide,n-octylquinoxalinium halide, n-decylquinoxalinium halide,n-dodecylquinoxalinium halide, n-tetradecylquinoxalinium halide,n-hexadecylquinoxalinium halide, n-hexylpyridopyridinium halide,n-octylpyridopyridinium halide, n-decylpyridopyridinium halide,n-dodecylpyridopyridinium halide, n-tetradecylpyridopyridininum halide,and n-hexadecylpyridopyridinium halide.

The preferred counter ions for the quaternary cationic salts arehalides, especially chloride and bromide. Particularly useful forpracticing the present invention are alkylbenzyldimethyl ammoniumchlorides, wherein the alkyl groups contain between 10 and 18 carbonatoms, and cetyldimethylethyl ammonium bromide. The useful range ofquaternary cationic salts in an effective amount of sterilant is fromabout 0.05% to 3% in actual use by weight.

Other counter ions, anions, useful in the practice of the presentinvention to neutralize the positive charge of the ammonium,phosphonium, sulfonium, or other positive moieties can be found in thefollowing list bicarbonate, bisulfite, fluoride, borate, carbonate,nitrite, nitrate, phosphite, phosphate, sulfite, sulfate, chloride,hypochlorite, chlorite, chlorate, perchlorate, hydroxide, fluoborate,iodide, iodate, periodate, and bromate.

The solubility of the various solutes in the novel sterilant of theinstant invention is improved by using small amounts of alkanols havingfrom one to six carbon atoms and/or glycols having from two to fourcarbon atoms. These alkanols and glycols also have concomitant andperipheral biocidal effect. Especially useful alkanols are methanol,ethanol, and isopropyl alcohol. Especially useful polyols are glycolssuch as ethylene glycol, propylene glycol, diethylene glycol, as well asglycerine. In the diluted solution for actual use, the effective amountfor the alkanol is from about 0.1% to 3% by weight, and the effectiveamount for the polyol or glycol is from about 0.1% to 3% by weight.

Other alcohols having eight or less carbon atoms useful in the practiceof the present invention are: 1-propanol, 1-butanol, 2-butanol,2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol,3-pentanol, 2-methyl-2-butanol, 2-methyl-3-butanol, 2-methyl-4-butanol,2,2-dimethyl-1-propanol, 1-hexanol, 2-hexanol, 3-hexanol,2,2-dimethyl-3-butanol, 2,2-dimethyl-4-butanol, 2,3-dimethyl-2-butanol,2-methyl-l-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol,2-methyl-4-pentanol, 2-methyl-5-pentanol, 3-methyl-1-pentanol,3-methyl-2-pentanol, 3-methyl-3-pentanol, 2,2-diethyl-1-ethanol,1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol,2,2,3-trimethyl-3-butanol, 2,3-dimethyl-3-pentanol,2,4-dimethyl-3-pentanol, 3-ethyl-1-pentanol, 3-ethyl-2-pentanol,3-ethyl-3-pentanol, 4-ethyl-1-pentanol, 4-ethyl-2-pentanol,4-ethyl-3-pentanol, 2-ethyl-1-pentanol, 2-methyl-1-hexanol,2-methyl-2-hexanol, 2-methyl-3-hexanol, 2-methyl-4-hexanol,3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1-hexanol,3-methyl-2-hexanol, 4-methyl-2-hexanol, 3-methyl-3-hexanol,3-methyl-4-hexanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol,2-methyl-1-heptanol, 3-methyl-1-heptanol, 4-methyl-1-heptanol,5-methyl-1-heptanol, 5-methyl-1-heptanol, 6-methyl-1-heptanol,2-methyl-2-heptanol, 3-methyl-2-heptanol, 4-methyl-2-heptanol,5-methyl-2-heptanol, 6-methyl-2-heptanol, 2-methyl-3-heptanol,3-methyl-3-heptanol, 4-methyl-3-heptanol, 5-methyl-3-heptanol,6-methyl-3-heptanol, 2-methyl-4-heptanol, 3-methyl-4-heptanol,4-methyl-4-heptanol, 5-methyl-4-heptanol, 6-methyl-4heptanol,2,2-dimethyl-1-hexanol, 3,3-dimethyl-1-hexanol, 4,4-dimethyl-1-hexanol,5,5 -dimethyl-1-hexanol, 2,3-dimethyl-1-hexanol, 2,4-dimethyl-1-hexanol,2,5-dimethyl-1-hexanol, 3,4-dimethyl-1-hexanol, 3,5-dimethyl-1-hexanol,2-ethyl-1-hexanol, 3-ethyl-1-hexanol, 4-ethyl-1-hexanol, and5-ethyl-1-hexanol.

Other glycols having eight or less carbon atoms useful in the practiceof the present invention are: 1,2-propanediol, 1,2-butanediol,1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol,2,methyl-1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol,1,4-pentanediol, 1,5-pentanediol, 2-methyl-1,2-butanediol,2-methyl-1,3-butanediol, 2-methyl-1,4-butanediol,2-methyl-2,3-butanediol, 2-methyl-3,4-butanediol, 1,2-hexanediol,1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol,2-methyl-1,2-pentanediol, 2-methyl-1,3-pentanediol,2-methyl-1,4-pentanediol, 2-methyl-1,5-pentanediol,2-methyl-2,3-pentanediol, 2-methyl-2,3-pentanediol,2-methyl-2,4-pentanediol, 2-methyl-2,5-pentanediol,2-methyl-3,4-pentanediol, 2-methyl-3,5-pentanediol,2-methyl-4,5-pentanediol, 2,3-dimethyl-1,2-butanediol,2,3-dimethyl-1,3-butanediol, 2,3-dimethyl-1,4-butanediol,2,3-dimethyl-2,3-butanediol.

Certain salts with anions at less than full oxidation state, such asnitrite, bisulfite, or chlorite, may be optionally employed in the novelsterilant solution of the instant invention to prevent corrosion, aswell as for their biocidal activity.

Also useful in the practice of the present invention are cations whereinthe metal oxidation state is lower than its chemically possible maximum.

Some useful compounds with less than full oxidation states are found inthe following salts first some with reduced anions and then some saltswith less oxidized cations, as follows: sodium phosphite, sodiumsulfite, sodium hypochlorite, sodium chlorite, sodium chlorate, sodiumselenite, sodium arsenite, sodium hypobromite, sodium bromite, sodiumbromate, sodium stannite, sodium antimonite, sodium tellurite, sodiumferrocyanide, sodium manganite, sodium manganate, potassium phosphite,potassium, sulfite, potassium hypochorite, potassium chlorite, potassiumchlorate, potassium selenite, potassium arsenite, potassium hypobromite,potassium bromite, potassium bromate, potassium stannite, potassiumantimonite, potassium tellurite, potassium ferrocyanide, potassiummanganite, potassium manganate, lithium phosphite, lithium sulfite,lithium hypochlorite, lithium chlorite, lithium chlorate, lithiumselenite, lithium arsenite, lithium hypobromite, lithium bromite,lithium bromate, lithium stannite, lithium antimonite, lithiumantimonite, lithium tellurite, lithium ferrocyanide, lithium manganite,lithium manganate, rubidium nitrite, rubidium phosphate, rubidiumsulfite, rubidium hypochlorite, rubidium chlorite, rubidium chlorate,rubidium selenite, rubidium arsenite, rubidium hypobromite, rubidiumbromite, rubidium bromate, rubidium stannite, rubidium antimonite,rubidium tellurite, rubidium ferrocyanide, rubidium manganite, rubidiummanganate, cesium nitrite, cesium phosphite, cesium sulfite, cesiumhypochlorite, cesium chlorite, cesium chlorate, cesium selenite, cesiumarsenite, cesium hypobromite, cesium bromite, cesium bromate, cesiumstannite, cesium antimonite, cesium telurite, cessium ferrocyanide,cesium manganite, cesium manganate, ferrous ferrocyanide, ferrousferricyanide, cuprous chloride, ferrous phosphate, stannous chloride,ferrous sulfate, manganous sulfate, plumbous sulfate, and chromouschloride.

Particularly useful are sodium, potassium, lithium, and ammonium saltsof nitrite, bisulfite, and chlorite; especially useful is sodiumnitrite. These optional salts may be employed in the range from 0.05% toabout 2.0% by weight of the actual solution employed.

A chelating agent may be optionally employed in the broad-spectrumsterilant of the present invention from 0% to 0.025% by weight to aid insolubility of the other components, to counteract any deleteriouseffects from diluting concentrated commercial strengths with hard waterfor use, and to help break down the coatings of spores, which have ahigh concentration of multivalent ions. The preferred chelating agent topractice the current invention may range from 0% to 0.025% by weight andis ethylene diamine tetraacetic acid (EDTA). Partial esters or salts ofEDTA may also be used. An example of a salt of EDTA is tetrasodiumethylenediamine tetraacetate.

Other useful chelating agents may be found in the following acids, fullsalts, or partial salts of: oxalic acid, malonic acid, oxaldihydrixamicacid, diaminoglyoxime, dithiomalonic acid, glyoxime, maleic acid,fumaric acid, oxalacetic acid, diglycolic acid, tartaric acid,oxalenediuramidoxime, thiodiglycolic acid, iminodiacetic acid,nitrilotriacetic acid, dimethylglyoxime, hydrazine-N,N'-diacetic acid,citraconic acid, itaconic acid, 2,4-pentanedione, glutaric acid,N-methyliminodiacetic acid, glutamic acid, aconitric acid (trans),gluconic acid, 1,2-cyclohexanediamine-N,N,N'-tetraacetic acid(cis&trans), 1,2-ethylenediamine-N,N,N',N'-tetraacetic acid,N'-benzylethylene-diamine-N,N,N'-triacetic acid,diethylenetriamine-N,N,N',N",N"-pentaacetic acid,hexamethyldiamine-N,N,N',N'-tetraacetic acid,2,2"-ethylenedioxybis(ethyliminodiacetic acid), 2,2'-oxybis(propyliminodiacetic acid), triethylenetetraminehexaacetic acid,1,3,5-triaminocyclohexanehexaacetic acid, and ethyl acetoacetate.

A dialdehyde containing up to six carbon atoms is a component of thebroad-spectrum sterilant of the present invention. Dialdehydes includemalonaldehyde, succinaldehyde, oxaldehyde (glyoxal), adipaldehyde, andpreferably glutaraldehyde. Alternatively, these compounds may be termedaliphatic dials, e.g. 1,5 pentanedial. By themselves, these compoundsare effective germicides to some degree, at high pH, but they fail tohave the wide breadth and speed of killing of the mixture of the currentinvention. This is especially true for the killing of the sporulentbacteria, where the dialdehydes alone can take up to ten hours to killspores, and for many viruses, where dialdehydes are ineffective. In thefinal dilution as used, in the present invention, an effective amount ofthe dialdehyde is from about 0.5% to about 7% by weight. A concentrationof dialdehyde of about 2.6 to 5 weight % is preferred and aconcentration of dialdehyde of 3.2 weight % is especially preferred.

Some useful dialdehydes in the practice of the present invention are thefollowing compounds and their mixtures: 1,2-ethanedial, 1,3-propanedial,1,4-butanedial, 1,5-pentanedial, 2-methyl-1,4-butanedial,2-methyl-1,3-propanedial, 2,2-dimethyl-1,3-propanedial,2,3-dimethyl-1,4-butanedial, 2,2-dimethyl-1,4-butanedial, 1,6hexanedial, 2-methyl-1,5-pentanedial, 3-methyl-1,5pentanedial,2-ethyl-1,3-propanedial, and 2-n-propyl-1,3-propanedial. Some examplesof heterocyclic dialdehydes are furan-2,5-dialdehyde,furan-3,4-dialdehyde, thiophene-2,5-dialdehyde,thiophene-3,4-dialdehyde, pyrrole-2,5-dialdehyde,pyrrole-3,4-dialdehyde, imidazole-4,5-dialdehyde,pyrazole-3,4-dialdehyde, 1,2,3-triazole-4,5-dialdehyde,pyrazine-2,3-dialdehyde, pyrimidine-4,5-dialdehyde,pyridazine-3,4-dialdehyde, pyridazine-4,5-dialdehyde. Aliphaticdialdehydes are preferred, but heterocyclic dialdehydes such as thosenamed above may also be employed.

As a practical matter, it is preferred to produce the broad-spectrumsterilant of the present invention in the form of one or moreconcentrated solutions prior to transport and storage. Theconcentrations of these solutions would be 50 to 100-fold higherstrength than the actual use-strengths given above. After transport andstorage, the user, normally a medical or dental technician, will dilutethe concentrate to produce an effective amount at the ultimate dilutionand then add the dialdehyde.

In concentrated form, a preferred embodiment of the sterilantconcentrate of the present invention would have the followingapproximate concentrations by weight:

    ______________________________________                                                               Weight %                                               ______________________________________                                        Alkyl*benzyldimethylammonium chloride                                                                  7                                                    *50% C-12, 30% C-14, 17% C-16, 3% C-18                                        Cetyldimethylethylammonium bromide                                                                     7                                                    Isopropyl alcohol        14                                                   Propylene glycol         12                                                   Sodium nitrite           7                                                    EDTA                     1.5                                                  Water, balance up to 100%                                                     ______________________________________                                    

In actual practice, the user will have prepared a desired quantity ofthe diluted sterilant concentrate by diluting the sterilant concentratewith distilled or tap water. This resulting solution will serve,further, as the diluent for the dialdehyde concentrate then to be addedthereto.

The diluted sterilant solution after combination is an exceptionallybroad-spectrum sterilant on a wide variety of metal, plastic,cross-linked resin, rubber, composite, coated, painted or natural wood,ceramic, or glass non-adsorbent surfaces, exemplified by but not limitedto the following: stainless steels (various), steels, not stainless(various), galvanized iron, copper, brass, aluminum, chromium platedmetals, tinned plating metals, enameled metals, polyethylene,polypropylene, polystyrene, acrylics, polyacetals, nylons, "epoxyresin"-coated wood, polyurethane-coated wood, alkyd resin painted wood,alkyd resin-coated metal, oil-based painted wood, phenol-formaldehyderesin laminates ("Formica" type), polyvinyl chloride-based furnituresurfaces ("Naugahyde" type), gum rubber surgical/dental adjuncts (dentaldam, tubing, catheters, gloves), hard rubber devices (bite blocks),water-based, latex-painted wood, glazed porcelain and other ceramics andvarious types of glass such as lime, flint, and borosilicates.

The present invention will now be described by reference to thefollowing examples, which are not to be deemed limitative of the presentinvention in any manner thereof.

EXAMPLE A

This example illustrates the preparation of an effective sterilizingamount of a final user solution of the sterilant composition of theinvention.

A 15 ml ampule of the above sterilant concentrate was diluted withdistiled water to a final volume of 1 liter. This was a dilution ratioof about 66.7:1. To this solution was added 50 ml of an aqueous 50% byweight solution of glutaraldehyde concentrate. On a weight basis, theconcentration of glutaraldehyde will be about 2.6% in the final usersolution.

Thus in the final user solution, the concentrations of the variouscomponents in the diluted sterilant will be as follows:

    ______________________________________                                                              Wt. %                                                   ______________________________________                                        Alkylbenzyldimethylammonium chloride                                                                  0.1                                                   Cetyldimethylethylammonium bromide                                                                    0.1                                                   Isopropyl alcohol       0.2                                                   Propylene glycol        0.16                                                  Sodium nitrite          0.1                                                   EDTA                    0.02                                                  Dialdehyde, esp. glutaraldehyde                                                                       2.6                                                   Water                   balance                                               ______________________________________                                    

The diluted sterilant composition of the present invention may beemployed over a wide, useful pH range from about pH 4 to about pH 9. Thepreferred range for use is from about pH 5 to about pH 8. This is inmarked contrast to the use of alkalinized dialdehydes alone, which areeffective only from about pH 7 to about pH 8.5. Although buffers mayoptionally be employed to keep the sterilant of the instant inventionwithin a narrow pH range, no buffer is necessary to practice thisinvention.

EXAMPLE B

This example illustrates the preparation of an effective sterilizingamount of a final user solution of the sterilant composition of theinvention.

A 15 ml ampule of the above sterilant concentrate was diluted withdistilled water to a final volume of 750 ml. This was a dilution ratioof about 50: 1. To this solution was added 50 ml of an aqueous 50% byweight solution of glutaraldehyde concentrate. On a weight basis, theconcentration of glutaraldehyde will be about 3.2% in the final usersolution.

Thus, in the final user solution, the concentrations of the variouscomponents in the diluted sterilant will be as follows:

    ______________________________________                                                              Wt. %                                                   ______________________________________                                        Alkylbenzyldimethylammonium chloride                                                                  0.15                                                  Cetyldimethylethylammonium bromide                                                                    0.15                                                  Isopropyl alcohol       0.25                                                  Propylene glycol        0.20                                                  Sodium nitrite          0.15                                                  EDTA                    0.025                                                 Dialdehyde, esp. glutaraldehyde                                                                       3.2                                                   Water                   balance                                               ______________________________________                                    

The diluted sterilant composition of the present invention may beemployed over a wide, useful pH range from about pH 4 to about pH 9. Thepreferred range for use is from about pH to about pH 8. This is inmarked contrast to the use of alkalinized dialdehydes alone, which areeffective only from about pH 7 to about pH 8.5. Although buffers mayoptionally be employed to keep the sterilant of the instant inventionwithin a narrow pH range, no buffer is necessary to practice thisinvention.

EXAMPLE 1

This example illustrates the effectiveness of the sterilant compositionof EXAMPLE A for nonsporulating bacteria.

The novel sterilant of the present invention was prepared with 400 ppmhard water as the diluent for test purposes:

    ______________________________________                                                              Wt. %                                                   ______________________________________                                        Alkylbenzldimethylammonium chloride                                                                   0.1                                                   Cetyldimethylethylammonium bromide                                                                    0.1                                                   Isopropyl alcohol       0.2                                                   Propylene glycol        0.16                                                  Sodium nitrate          0.11                                                  EDTA                    0.02                                                  Glutaraldehyde          2.60                                                  Water                   balance                                               ______________________________________                                    

Employing the Use-Dilution Method of the Association of OfficialAgricultural Chemists (AOAC) 60 ring carriers were tested on threebatchs each for efficacy against the following organisms (US EPAProcedure DIS/TSS-1 and 2 of January 1982 ); Salmonella choleraesiusATCC 10708 (Gram-negative) , Staphllococcs aureus ATCC 6538(Gram-positive), and Pseudomonas aeruginosa ATCC 15442 (Gram-positive,nosocomial pathogen).

All these microorganisms were killed within 10 minutes at 20 degrees C.

EXAMPLE 2

This example illustrates the efficacy of the broad-spectrum sterilant ofthe present invention for killing sporulating bacteria.

The novel sterilant solution was prepared as in EXAMPLE 1 for testingagainst Gram-positive, sporulating bacteria Bacillus subtilus ATCC 19659and Clostridium sporogenes ATCC 3584 employing US EPA ProcedureDIS/TSS-9 of April 1981 (AOAC Sporicidal Test). Sixty carriers for eachtype of surface, porcelain penicylinders and silk suture loops, for eachof three samples for each of three batches involved a total of 720carriers.

As required, all microorganisms were killed on all carriers in about 5hours, less than e hours at 20 degrees C.

In a similar test alkalinized glutaraldehyde can meet this standard onlyafter 10 hours of contact.

EXAMPLE 3

This example illustrates the efficacy of the broad-spectrum sterilant ofthe present invention for killing fungi and fungal spores.

The novel sterilant solution was prepared as in EXAMPLE 1 for testingagainst pathogenic fungus Trichophyton mentagrophytes ATCC 27289according to the AOAC Fungicidal Test by EPA procedure DIS/TSS-6 ofAugust 1981. For this fungus two batches were used for two samples eachkilling all organisms within 10 minutes at 20 degrees C.

EXAMPLE 4

This example illustrates the efficacy of the broad-spectrum sterilant ofthe present invention in killing viruses, some of which none of thecomponents of the novel sterilant can kill individually under the sameconditions.

The novel sterilant solution was prepared as in EXAMPLE 1 for testingagainst the following viruses: Herpes Simplex I and II, Coxsackie virusB1, Coxsackie virus A9, Vaccinia Virus, Influenza virus A, Adenos virusII, Poliovirus I, Rhino virus, Cytomegalo virus, and Corona virus, allaccording to EPA procedure DIS/TSSD-7. For two batches each, fourreplicates were carried by ten-fold dilution and measured to three-logdiminution. After incubation, the samples were recovered afteradsorption time on mammalian cell monolayers.

The novel sterilant inactivated all the viruses within 10 minutes at 20degrees C. It is known that alkalinized glutaraldehyde fails toinactivate at least Coxsackie virus and Poliovirus I under theseconditions.

This example illustrates the effectiveness of the sterilant compositionof EXAMPLE B for nonsporulating bacteria.

The novel sterilant of the present invention was prepared with 400 ppmhard water as the diluent for test purposes:

    ______________________________________                                                              Wt. %                                                   ______________________________________                                        Alkylbenzyldimethylammonium chloride                                                                  0.15                                                  Cetyldimethylethylammonium bromide                                                                    0.15                                                  Isopropyl alcohol       0.25                                                  Propylene glycol        0.20                                                  Sodium nitrite          0.15                                                  EDTA                    0.025                                                 Glutaraldehyde          3.2                                                   Water                   balance                                               ______________________________________                                    

Employing the Use-Dilution Method of the Association of OfficialAgricultural Chemists (AOAC) 60 ring carriers were tested on threebatchs each for efficacy against the following organisms (US EPAProcedure DIS/TSS-1 and 2 of January 1982 ); Salmonella choleraesiusATCC 10708 (Gram-negative), Staphylococcus aureus ATCC 6538(Gram-positive), and Pseudomonas aeruginosa ATCC 15442 (Gram-positive,nosocomial pathogen).

All these microorganisms were killed within 10 minutes at 20 degrees C.

EXAMPLE 6

This example illustrates the efficacy of the broad-spectrum sterilant ofthe present invention for killing sporulating bacteria.

The novel sterilant solution was prepared as in EXAMPLE 5 for testingagainst Gram-positive, sporulating bacteria Bacillus subtilus ATCC 19659and Clostridium sporogenes ATCC 3584 employing US EPA ProcedureDIS/TSS-9 of April 1981 (AOAC Sporicidal Test) . Sixty carriers for eachtype of surface, porcelain penicylinders and silk suture loops, for eachof three samples for each of three batches involved a total of 720carriers.

As required, all microorganisms were killed on all carriers in about 5hours, less than 6 hours at 20 degrees C.

In a similar test alkalinized glutaraldehyde can meet this standard onlyafter 10 hours of contact.

EXAMPLE 7

This example illustrates the efficacy of the broad-spectrum sterilant ofthe present invention for killing fungi and fungal spores.

The novel sterilant solution was prepared as in EXAMPLE 5 for testingagainst pathogenic fungus Trichophyton mentagrophytes ATCC 27289according to the AOAC Fungicidal Test by EPA procedure DIS/TSS -6 ofAugust 1981. For this fungus two batches were used for two samples eachkilling all organisms within 10 minutes at 20 degrees C.

EXAMPLE 8

This example illustrates the efficacy of the broad-spectrum sterilant ofthe present invention in killing viruses, some of which none of thecomponents of the novel sterilant can kill individually under the sameconditions.

The novel sterilant solution was prepared as in EXAMPLE 5 for testingagainst the following viruses: Herpes Simplex I and II, Coxsackie virusB1, Coxsackie virus A9, Vaccinia Virus, Influenza virus A, Adenos virusII, Poliovirus I, Rhino virus, Cytomegalo virus, and Corona virus, allaccording to EPA procedure DIS/TSSD-7. For two batches each, fourreplicates were carried by ten-fold dilution and measured to three-logdiminution. After incubation, the samples were recovered afteradsorption time on mammalian cell monolayers.

The novel sterilant inactivated all the viruses within 10 minutes at 20degrees C. It is known that alkalinized glutaraldehyde fails toinactivate at least Coxsackie virus and Poliovirus I under theseconditions.

The sterilant composition of the present invention has the advantages ofbeing effective to kill a broad spectrum of microorganisms very rapidlywith low concentrations of the active ingredients. The sterilantcomposition as a combination of ingredients is more effective againstseveral microorganisms together at the same time than would be possibleby using each active ingredient separately against the combination ofmicroorganisms.

The sterilants of the disclosure above exemplified by the preferredembodiments of the various Examples are effective against a wide varietyof microorganisms such as those of Tables I throuqh VII.

                  TABLE I                                                         ______________________________________                                        VIRUSES                                                                       ______________________________________                                        ADENOVIRUSES      Feline stomatitis                                           Avian adenovirus Types 1-10                                                                     CORONAVIRUSES                                               Marble spleen disease virus                                                   Bovine adenovirus Types 1-8                                                                     Calf diarrheal coronavirus                                  Canine adenovirus Canine coronavirus                                          Infectious canine hepatitis                                                                     Feline infectious                                           Human adenovirus Types 1-41                                                                     peritonitis                                                 Mouse adenovirus  Hemagglutinating                                            Swine adenovirus  encephalomyelitis                                           Baboon adenovirus Human coronavirus                                           Chimpanzee adenovirus                                                                           Infectious bronchitis                                       Simian adenovirus Mouse hepatitis virus                                       Types 1-39        Rabbit coronavirus                                                            Rat coronavirus                                             ARENAVIRUSES      Sialodacryoadenitis virus                                                     Transmissible                                               Amapari           gastroenteritis                                             Junin             Turkey enteritis                                            Latino            coronavirus                                                 Lymphocytic                                                                   choriomeningitis  FLAVIVIRUSES                                                Bolivian Hemorrhagic Fever                                                    Parana            Banzi                                                       Pichinde virus    Bukalasa                                                    Tacaribe virus    Bussuquara                                                  Tamiami virus     Cowbone ridge                                                                 Dakar bat                                                   BUNYAVIRIDAE      Dengue Types 1-4                                                              Edge Hill                                                   Anopheles Group   Entebbe bat                                                 Bunyamwera Super Group                                                                          Ilheus                                                      Bwamba Group      Japanese encephalitis                                       California Group  Kokobera                                                    Capim Group       Kyasanur                                                    Gamboa Group      Louping III                                                 Guama Group       Modoc                                                       Koongol Group     Montana myotis                                              Patois Group      leukoencephalitis                                           Simbu Group       Murray Valley encephalitis                                  Tete Group        Ntaya                                                       Turlock Group     Powassan                                                    Phleboviruses     Rio Bravo                                                   Nairoviruses      Russian spring-summer                                       Hantaviruses      encephalitis                                                                  Sepik                                                       CALICIVIRUSES     Simian hemorrhagic fever                                                      St. Louis encephalitis                                      Feline conjunctivitis                                                                           Stratford                                                   Feline picornavirus                                                                             Tenbusu                                                     Cganda S          Blue tongue all types                                       West Nile         Changuinola                                                 Yellow fever      Colorado tick fever                                         Zika              Corriparta                                                                    Epizootic hemorrhagic                                       HERPESVIRUSES     disease of deer                                                               Ieri                                                        Avian laryngotracheitis                                                                         Irituia                                                     Duck enteritis    Lebombo                                                     Falcon herpesvirus                                                                              Tribec                                                      Lake Victoria cormorant                                                                         Wad Medani                                                  Marek's disease                                                               Parrot herpesvirus                                                                              ORTHOMYXOVIRUSES                                            Pigeon herpesvirus                                                            Turkey herpesvirus                                                                              Avian Influenza                                             Bovine herpesvirus                                                                              Horse Influenza A                                           Infectious bovine Human Influenza                                             rhinotracheitis   A, B & C                                                    Canine herpesvirus                                                                              Swine Influenza                                             Equine cytomegalovirus                                                                          Thogoto                                                     Equine herpesvirus                                                            Feline herpesvirus                                                                              PAPOVAVIRUSES                                               Feline rhinotracheitis virus                                                  Channel catfish   Human polyoma                                               Herpesvirus salmonis                                                                            Bovine papilloma                                            Guinea pig herpes-like virus                                                                    Human papilloma                                             Guinea pig salivary gland                                                                       JC virus                                                    virus             K-virus                                                     Guinea pig X virus                                                                              Lymphotropic Papovavirus                                    Burkitt's lymphoma                                                                              Papilloma                                                   Cytomegalovirus   Polyoma                                                     Herpes simplex Types 1 & 2                                                                      Simian Papovavirus                                          Varicella         SV-40                                                       Varicella-Zoster                                                              B Virus           PARAMYXOVIRUSES                                             Hepatitis A, B & C virus                                                      Herpesvirus aotus Bluegill                                                    Herpesvirus ateles                                                                              Bovine morbillivirus-like                                   Herpesvirus saguinus                                                                            Bovine respiratory                                          Herpesvirus saimiri                                                                             syncytial virus                                             Monkey cytomegalovirus                                                                          Canine distemper                                            Simian herpesvirus 2 & 3                                                                        Canine parainfluenza                                        Squirrel monkey   Fer de Lance virus                                          cytomegalovirus   Measles                                                     Pseudorabies      Mumps                                                       Caprine herpesvirus                                                                             Nariva                                                      Frog Virus 4      Newcastle disease                                           Mouse Salivary Gland Virus                                                                      Parainfluenza                                               Rabbit herpesvirus                                                                              Pneumonia virus of mice                                                       Respiratory syncytial                                       ORBIVIRUSES       Simian paramyxovirus                                                          Subacute sclerosing                                         panencephalitis   Swine pox                                                   Yucaipa           Tanapox                                                                       Vaccinia                                                    PARVOVIRUSES      Yabu tumor poxvirus                                         Adeno-associated virus                                                                          REOVIRUSES                                                  Aleutian disease                                                              Avian adeno-associated                                                                          Avian reovirus, all types                                   Bovine parvovirus Feline reovirus                                             Canine parvovirus Reovirus, all types                                         Feline panleukopenia                                                                            Turkey enteric reovirus                                     Hemorrhagic encephalopathy                                                    Porcine parvovirus                                                                              RETROVIRUSES                                                PICORNAVIRUSES    Avian leukosis-sarcoma                                                        complex                                                     Poliovirus 1, 2 & 3                                                                             Avian reticuloendotheliosis                                 Coxsackievirus, all types                                                                       group                                                       Echovirus, all types                                                                            Feline leukemia group                                       Enterovirus, all types                                                                          Murine leukemia-sarcoma                                     Human rhinovirus, all types                                                                     group                                                       Avian encephalomyelitis                                                                         Bovine syncytial virus                                      Baboon enterovirus                                                                              Caprine arthritis-                                          Bovine enterovirus,                                                                             encephalitis virus                                          all types         Feline syncytia-forming                                     Bovine rhinovirus,                                                                              Human T-cell lukemia virus                                  all types         Human immunodeficiency                                      Encephalomyocarditis                                                                            virus                                                       Mouse encephalomyelitis                                                                         Mouse mammary tumor                                         Porcine enterovirus,                                                                            Simian foamyvirus                                           all types         Squirrel monkey retrovirus                                  Rat encephalomyelitis                                                                           Syncytium-forming virus                                     Simian picornavirus,                                                                            of Marmosets                                                all types         Visna virus                                                 POXVIRUSES        RHABDOVIRUSES                                               Alastrim (Variola minor)                                                                        Aruac                                                       Bovine papular stomatitis                                                                       Bovine paralytic rabies                                     Canary pox        Chaco                                                       Cotia             Chandipura                                                  Cowpox            Cocal virus                                                 Embu              Hart virus                                                  Fibroma           Infectious hematopoietic                                    Fowlpox           necrosis                                                    Milker's nodule virus                                                                           Jurona                                                      Monkeypox         Kern Canyon                                                 Myxoma            Klamath                                                     Rabbit fibroma    Kwatta                                                      Rabbitpox         Lagos bat                                                   Raccoonpox        March                                                       Smallpox          Mokola                                                      Mossuril          Venkatapuram                                                Mount Elgon bat   Wanowrie                                                    Navorro           PLANT VIRUSES                                               Piry virus        Agropyron Mosaic                                            Rabies            Alfalfa Mosaic                                              Sawgrass          Apple Chlorotic                                             Timbo             Apple Mosaic                                                Vesicular stomatitis                                                                            Artichoke Latent                                                              Barley Stripe Mosaic                                        ROTAVIRUSES       Barley Yellow Dwarf                                                           Bean Common Mosaic                                          Bovine rotavirus  Bean Golden Mosaic                                          Calf rotavirus    Bean Pod Mottle                                             Human rotavirus   Bearded Iris Mosaic                                         Porcine pararotavirus                                                                           Beet Curly Top                                              Porcine rotavirus Beet Mosaic                                                 Rhesus rotavirus  Beet Western Yellows                                        Simian rotavirus  Belladonna Mottle                                                             Bidens Mottle                                               TOGAVIRUSES       Broad Bean                                                                    Broccoli Necrotic                                           Alphavirus group  Carnation Mottle                                            Pestiviruses      Cherry Leaf Rool                                            Rubeviruses       Chrysanthemum Aspermy                                                         Citrange Stunt                                              UNCLASSIFIED VIRUSES                                                                            Cowpea Chlorotic Mottle                                                       Desmodium Yellow Mottle                                     Anaplasma marginale                                                                             Elm Mosaic                                                  Creutzfeldt-Jakob Glycine Mottle                                              Duck hepatitis    Grapevine Fanleaf                                           Eretmapodites     Henbane Mosaic                                              Equine infectious anemia                                                                        Lettuce Mosaic                                              virus             Lychnis Ringspot                                            Frog virus 3      Maize rough Dwarf                                           Golden shine virus                                                                              Myrobalan Latent Ringspot                                   Grunt fin agent   Nasturtium Ringspot                                         Hepatitis A virus Oat Blue Dwarf                                              Hepatitis B virus Onion Yellow Dwarf                                          Ichampadi         Pangola Stunt                                               Infectious bursal disease of                                                                    Panicum Mosaic                                              chickens          Passionfruit Woodiness                                      Infectious pancreatic                                                                           Peanut Stunt                                                necrosis of trout Plantago Mottle                                             Infectious pancreatic                                                                           Poa Semilatent                                              necrosis virus    Pokeweed Mosaic                                             Kuru              Prunus Necrotic Ringspot                                    Lymphocystis      Raspberry Bushy Dwarf                                       Matucare          Scophularia Mottle                                          Nodamura virus    Tobacco Mosaic                                              Quaranfil         Tomato Aspermy                                              Tadpole edema virus                                                                             Tulip Breaking                                              Tembe             Watermelon Mosaic                                           White Clover Mosaic                                                           Wound Tumor                                                                   ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        MISCELLANEOUS ORGANISMS                                                       ______________________________________                                                  Chlamydia psittaci                                                            Chlamydia trachomatis                                                         Coxiella burneti                                                              Ehrlichia risticii                                                            Rickettsia akari                                                              Richettsia canada                                                             Rickettsia conori                                                             Rickettsia montana                                                            Rickettsia mooseri                                                            Rickettsia prowazeki                                                          Rickettsia rickettsii                                                         Rickettsia sennetsu                                                           Rickettsia tsutsugamushi                                                      Rochalimaea quintana                                                          Rochalimaea vinsonii                                                          Thai tick typhus                                                              Wolbachia persica                                                   ______________________________________                                    

                  TABLE III                                                       ______________________________________                                        GRAM NEGATIVE BACTERIA                                                        ______________________________________                                        Acetobacter acet   Flavobacterium                                             Acholeplasma laidlawii                                                                           meningosepticum                                            Achromobacter viscosus                                                                           Francisella tularensis                                     Acidiphilium cryptum                                                                             Fusobacterium necrophorum                                  Acinetobacter calcoaceticus                                                                      Gardnerella vaginalis                                      Acinetobacter anatratus                                                                          Haemophilus aegyptius                                      Acinetobacter lwoffii                                                                            Hafnia alvei                                               Actinomyces bovis  Klegsiella oxytoca                                         Actinomyces israelii                                                                             Klebsiella pneumoniae                                      Actinomyces pyogenes                                                                             Legionella cherrii                                         Actinoplanes violaceus                                                                           Legionella feelei                                          Aeromonas hydrophila                                                                             Legionella pneumophila                                     Aeromonas salmonicida                                                                            Leptospira biflexa                                         Agrobacterium tumefaciens                                                                        Moraxella phenylpyruvica                                   Alcaligenes denitrificans                                                                        Morganella morganii                                        Alcaligenes faecalis                                                                             Mycoplasma canis                                           Anaerorhabdus furcosus                                                                           Mycoplasma hyorhinis                                       Aquaspirillum anulus                                                                             Mycoplasma pneumoniae                                      Arachnia propionica                                                                              Neisseria gonorrhoea                                       Arthrobacter ilicis                                                                              Neisseria meningitidis                                     Azotobacter beijerinckii                                                                         Oligella urethralis                                        Bacteroides bivius Pasteurella multocida                                      Bacteroides fragilis                                                                             Proteus mirabilis                                          Bacteroides levii  Proteus vulgaris                                           Bdellovibrio solpii                                                                              Providencia rettgeri                                       Beggiatoa alba     Providencia rustigianii                                    Beijerinckia indica                                                                              Providencia stuartii                                       Bifidobacterium boum                                                                             Pseudomonas aeruginosa                                     Bordetella bronchiseptica                                                                        Pseudomonas avenae                                         Bordetella pertussis                                                                             Pseudomonas cepacia                                        Borrrelia burgdorferi                                                                            Pseudomonas pseudomallei                                   Brucelia abortus   Pseudomonas putida                                         Campylobacter coli Salmonella choleraesuis                                    Campylobacter jejuni                                                                             Salmonella typhi                                           Campylobacter pylori                                                                             Salmonella typhimurium                                     Chlamydia psittaci Serratia liquefaciens                                      Chlamydia trachomatis                                                                            Serratia marcescens                                        Chromobacterium violaceum                                                                        Shigella boydi                                             Citrobacter freundii                                                                             Shigella dysenteriae                                       Comamonas terrigena                                                                              Shigella flexneri                                          Deleya aesta       Shigella sonnei                                            Deleya venusta     Thiobacillus thiooxidans                                   Dermatophilus congolensis                                                                        Treponema hyodysenteriae                                   Edwardsiella tarda Treponema pallidum                                         Eikenella corrodens                                                                              Ureplasma gallorale                                        Enterobacter aerogenes                                                                           Veillonella caviae                                         Enterococcus avium Vibrio cholerae                                            Enterococcus faecalis                                                                            Wolinella succinogenes                                     Enterobacter cloacae                                                                             Xanthobacter flavus                                        Erwinia citreus    Xanthomonas campestris                                     Escherichia coli   Yersinia pestis                                            Ewingella americana                                                                              Zymomonas mobilis                                          ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                        GRAM POSITIVE BACTERIA                                                        ______________________________________                                        Deinococcus erythromyxa                                                                          Mycobacterium bovis                                        Deinococcus proteolyticus                                                                        Mycobacterium fortuitum                                    Erysipelothrix insidiosa                                                                         Mycobacterium                                              Erysipelothrix rhusiopathiae                                                                     intracellulare                                             Eubacterium aerofaciens                                                                          Mycobacterium leprae                                       Eubacterium angustum                                                                             Mycobacterium tuberculosis                                 Eubacterium combessi                                                                             Norcardia asteroides                                       Eubacterium eligens                                                                              Norcardia brasiliensis                                     Eubacterium fosser Paracoccus denitrificans                                   Jonesia denitrificans                                                                            Pediococcus dextrinicus                                    Kurthia gibsonii   Peptostreptococcus                                         Lactobacillus agilis                                                                             asaccharolyticus                                           Lactobacillus brevis                                                                             Peptostreptococcus micros                                  Lactobacillus buchneri                                                                           Phormidium sp                                              Lactobacillus carnis                                                                             Planococcus citreus                                        Lactobacillus casei                                                                              Propionibacterium acnes                                    Lactobacillus divergens                                                                          Propionibacterium                                          Lactogacillus helveticus                                                                         freudenreichii                                             Lactobacillus jensenii                                                                           Rhodococcus equi                                           Lactobacillus kefir                                                                              Rhodococcus erythropolis                                   Lactobacillus xylosis                                                                            Sarcina maxima                                             Lactococcus garviae                                                                              Staphylococcus aureus                                      Lactococcus lactis Staphylococcus epidermidis                                 Lactococcus plantarum                                                                            Staphylococcus hominis                                     Leptothrix buccalis                                                                              Staphylococcus warneri                                     Leuconostoc lactis Stomatococcus                                              Leuconostoc mesenteroides                                                                        muchilaginosus                                             Leuconostoc oenos  Streptobacillus                                            Listeria grayi     moniliformis                                               Listeria innocua   Streptococcus dysgalactiae                                 Listeria monocytogenes                                                                           Streptococcus equi                                         Micrococcus agilis Streptococcus equisimilus                                  Micrococcus cryophilus                                                                           Streptococcus faecalis                                     Micrococcus halobius                                                                             Streptococcus pyogenes                                     Micrococcus luteus Streptomyces albulus                                       Mycobacterium aurum                                                                              Streptomyces vulgaris                                      Mycobacterium avium                                                           ______________________________________                                    

                  TABLE V                                                         ______________________________________                                        GRAM POSITIVE SPORE FORMING BACTERIA                                           Bacillus             Clostridium                                             ______________________________________                                        acidocaldarius       acetobutylicum                                           alcaophilus          acidiurici                                               alvei                aerotolerans                                             aminoglucosidicus    barkeri                                                  aneurinolyticus      beijerinckii                                             anthracis            bifermentans                                             badius               botulinum                                                brevis               cadaveris                                                capitovalis          carnis                                                   cereus               cellulolyticum                                           chitinosporus        chauvoei                                                 circulans            clostridiiforme                                          cirroflagellosus     coccoides                                                coagulans            collagenovorans                                          epiphytus            cylindrosporum                                           fastidiosus          difficile                                                filicolonicus        durum                                                    firmus               flavum                                                   freudenreichii       formicoaceticum                                          fructosus            haemolyticum                                             globiggi             hastiforme                                               globisporus          histolyticum                                             gordonae             indolis                                                  implexus             kaneboi                                                  insolitus            kluyveri                                                 laevolacticus        lentoputrescens                                          larvae               limosum                                                  laterosporus         lortetii                                                 lentimorbus          perfringens                                              lentus               putrificum                                               licheniformis        septicum                                                 megaterium           sordellii                                                mycoides             sporogenes                                               pumilus              tetani                                                   schlegelii           tetanomorphum                                            stearothermophilus   thermocellum                                             subtilis             thermolacticum                                           thuringiensis        tyrobutyricum                                            xerothermodurans     villosum                                                 ______________________________________                                    

                  TABLE VI                                                        ______________________________________                                        FUNGI                                                                         ______________________________________                                        Absidia blakesleeana                                                                            Entonaema liquescens                                        Achaetomium luteum                                                                              Epidermophyton floccosum                                    Achlya hypogyna   Filobasidiella neoformans                                   Aciculoconidium aculeatum                                                                       Fonsecaea pedrosoi                                          Acladium castellanii                                                                            Fusarium solani                                             Acemoniella lutzi Geotrichum candidum                                         Acrodontium salmoneum                                                                           Gibberella baccata                                          Actinodendron verticillatum                                                                     Gymnosporangium globosum                                    Actinomucor elegans                                                                             Histoplasma capsulatum                                      Acytostelium elipticum                                                                          Kluyveromyces wickerhamii                                   Aqaricus abruptibulbus                                                                          Madurella mycetomi                                          Agaricus campestris                                                                             Melampsora medusae                                          Akenomyces costatus                                                                             Microsporum canis                                           Alternaria alternata                                                                            Mucor hiemalis                                              Alternaria citri  Nectriella pironii                                          Armillaria limonea                                                                              Neurospora tetrasperma                                      Arthrobotrys oligospora                                                                         Paecilomyces lilacinus                                      Arthroderma benhamiae                                                                           Penicillium aurantiogriseum                                 Arthroderma gypseum                                                                             Phialophora richardsiae                                     Arthroderma incurvatum                                                                          Phycomyes nitens                                            Articulospora tetracladia                                                                       Pichia membranaefaciens                                     Aspergillus carneus                                                                             Pityrosporium ovale                                         Aspergillus fischeri                                                                            Pseudallescheria boydii                                     Aspergillus fumigatus                                                                           Puccinia graminis                                           Aspergillus niger Pyrenophora trichostoma                                     Aureobasidium mansonii                                                                          Rhizoctonia repens                                          Basidiobolus haptosporus                                                                        Rhizomucor pusillus                                         Blastobotrys aristata                                                                           Rhizopus microsporus                                        Blastomyces dermatitidis                                                                        Rhodotorula rubra                                           Blastoschizomyces capitatus                                                                     Rhynchosporium secalis                                      Botrytis squamosa Saccharomyces cerevisiae                                    Byssochlamys fulva                                                                              Sclerotium rolfsii                                          Candida albicans  Sporothrix schenckii                                        Candida tropicalis                                                                              Sporotrichum thermophile                                    Cephalosporium deformans                                                                        Stemphylium botryosum                                       Ceratocytis ulmi  Torula thermophila                                          Chaetomium globosum                                                                             Torulopsis pintolopesii                                     Chrysosporium pannorum                                                                          Trichoderma polysporum                                      Cladosporium carpophilum                                                                        Trichophyton mentagrophytes                                 Cladosporium resinae                                                                            Trichophyton rubrum                                         Coccidioides immitis                                                                            Ulocladium botrytis                                         Cronartium fusiforme                                                                            Uromyces phaseoli                                           Cryptococcus neoformans                                                                         Verticillium nigrescens                                     Curvularia prasadii                                                                             Xylohypha bantiana                                          Dictyostelium discoideum                                                                        Yarrowia lipolytica                                                           Zygosaccharomyces bailii                                    ______________________________________                                    

                  TABLE VII                                                       ______________________________________                                        PROTISTS- ALGAE/PROTOZOA                                                      ______________________________________                                        Acanthamoeba astronyxis                                                                         Leishmania hertigi                                          A. castellanii    Leishmania mexicana                                         A. culbertsoni    Leishmania tropica                                          A. hatchetti      Leptomonas pyrrhocoris                                      A. lenticulata    Lingulamoeba leei                                           A. polyphaga      Lohomonas piriformis                                        A. royreba        Monocercomonas colubrorum                                   Babesia microti   Muriella aurantiaca                                         Botrydium cystosum                                                                              Naegleria australiennsis                                    Cephaleuros virescens                                                                           Naegleria fowleri                                           Chalamydomonas dorsoventralis                                                                   Naegleria gruberi                                           Chlorella protothecoides                                                                        Naegleria jadini                                            Chlorella saccharophilia                                                                        Nosema necatrix                                             Chlorella sorokiniana                                                                           Ochromonas malhamensis                                      Chlorella variegata                                                                             Paramecium primaurelia                                      Chlorella xanthella                                                                             Paramecium                                                  Chlorella zopfingiensis                                                                         multimicronucleatum                                         Chlorogonium elongatum                                                                          Pentatrichoimonas hominis                                   Crithidia fasciculata                                                                           Plasmodium brasilianum                                      Diethamoeba fragilis                                                                            Plasmodium coatneyi                                         Dunaliella tertiolecta                                                                          Plasmodium cynomolgi                                        Entamoeba coli    Plasmodium falciparum                                       Entamoeba gingivalis                                                                            Plasmodium vivax                                            Entamoeba histolytica                                                                           Prototheca wickerhamii                                      Euglena gracilis  Tetracystis disociata                                       Giardia intestinalis                                                                            Tetrahymena borealis                                        Giardia lamblia   Tetrahymena thermophila                                     Haematococcus lacustris                                                                         Trichomonas gallinae                                        Hartmannella limax                                                                              Trichomonas vaginalis                                       Herpetomonas mariadeanei                                                                        Tritrichomonas foetus                                       Leishmania braziliensis                                                                         Trypanosoma brucei                                          Leishmania donovani                                                                             Trypanosoma cruzi                                           ______________________________________                                    

We claim:
 1. A biocidal, aqueous, composition for killing bacteria,spores, fungi, and viruses on nonabsorbent surface comprising:a) twoquaternary ammonium compounds, each in the amount of from about 0.05 to3 percent by weight, one of said two quaternary ammonium compounds is aheterocyclic quaternary ammonium compound, and the other of saidquaternary ammonium compounds is an aliphatic quaternary ammoniumcompound having an aromatic and an alkyl moiety or having a long chainaliphatic and a lower alkyl moiety; b) one aliphatic dialdehyde havingfrom 2 to 6 carbon atoms in the amount of from about 0.5 to about 7percent by weight; and c) at least one aliphatic hydroxyl compoundhaving from 1 to 8 carbon atoms in the amount from 0.1 to about 3percent by weight;all weight percents being in the final use dilution.2. The biocidal composition of claim 1, wherein the weight percent ofthe aliphatic dialdehyde in the final use dilution is in the amount offrom about 2.6 to about 5 weight percent.
 3. The biocidal composition ofclaim 1, further comprising a cheating agent in the amount of zero toabout 0.025 weight percent of the final use dilution.
 4. The biocidalcomposition of claim 3, wherein the cheating agent is tetrasodiumethylenediamine tetraacetate.
 5. The biocidal composition of claim 1,wherein the pH ranges from about 4 to about
 9. 6. The biocidalcomposition of claim 1, wherein the dialdehyde is 1,5-pentanedial(glutaraldehyde) comprising from 2.6 to 3.2 weight percent of the finaluse dilution.
 7. The biocidal composition of claim 1, wherein theheterocyclic quaternary ammonium compound is n-hexylpyridinium halide.8. The biocidal composition of claim 1, wherein the aliphatic quaternaryammonium compound contains an aromatic moiety which is benzylalkyl. 9.The biocidal composition of claim 1, wherein the aliphatic quaternaryammonium compound contains a long chain aliphatic moiety which iscetyldimethylethyl.
 10. The biocidal composition of claim 1, wherein thealiphatic hydroxy compound is selected from the group consisting ofisopropyl alcohol, propylene glycol, and their mixtures.
 11. Thebiocidal composition of claim 1, further comprising a soluble,inorganic, nitrite salt.
 12. The biocidal composition of claim 1,wherein all the all the quaternary ammonium compounds are halide salts.13. A method for sterilizing a nonabsorbent surface comprising the stepsof contacting said surface with an effective sterilizing amount of anaqueous composition comprising:a) two quaternary ammonium compounds,each in the amount of from about 0.05 to 3 percent by weight, one ofsaid two quaternary ammonium compounds is a heterocyclic quaternaryammonium compound, and the other of said quaternary ammonium compoundsis an aliphatic quaternary ammonium compound having an aromatic and analkyl moiety or having a long chain aliphatic and a lower alkyl moiety;b) one aliphatic dialdehyde having from 2 to 6 carbon atoms in theamount of from about 0.5 to about 7 percent by weight; and c) at leastone aliphatic hydroxyl compound having from one to eight carbon atoms inthe amount from about 0.1 to about 3 percent by weight;all weightpercents being in the final use dilution; and killing on said surfacebacteria, spores, fungi, and viruses.